Novel perfume compositions and perfumed articles containing di-lower alkyl and lower alkylene acetals of 2-and 3-phenyl pentenals

ABSTRACT

Perfume aroma augmenting compositions containing a quantity of at least one di-lower alkyl or lower alkylene acetal of a 2- and 3-phenyl-pentenal sufficient to alter the aroma and/or organoleptic characteristics of said compositions and perfume and perfumed materials containing at least one of said acetals.

United States Patent [191 Sehreiber et al.

I Nov. 25, 1975 NOVEL PERFUME COMPOSITIONS AND PERFUMED ARTICLESCONTAINING Dl-LOWER ALKYL AND LOWER ALKYLENE ACETALS OF Z-AND 3-PHENYLPENTENALS [75] Inventors: William Lewis Sehreiber, Jackson;

Manfred Vock, Locust, John B. Hall, Rumson, all of N.J.; Edward JosephShuster, New York, N.Y.; Alton Dewitt Quinn, Abrahamsville. Pa

[73} Assignee: International Flavors 8L Fragrances Inc., New York, N.Y.

1 Filed: Sept. 10, 1974 211 Appl. No.1 504,738

Related U.S. Application Data [62] Division of Serf No. 276,922, Aug. 1,I972 abandonedv {52] U.S. Cl. 252/522; 252/89; 424/76 [Sl] lnt. Cl. A61K7/46; C] lB 9/00 [58] Field of Search 252/89v 170, 522; 429/76 [56]References Cited UNITED STATES PATENTS 3.829504 8/l974 Hall et all252/522 3,862,340 l/l975 Schreiher et 252/522 3,879,425 4/l975 Hall etal. 252/522 Primary E.iarninerC. Davis Attorney, Age/ll 0r Firm-ArthurLi Liherman, Esq; Harold Haidt, Esq

[57] ABSTRACT Perfume aroma augmenting compositions containing aquantity of at least one di-lower alkyl or lower alkyl ene acetal of a2- and 3'phenyl-pentenal sufficient to alter the aroma and/ororganoleptic characteristics of said compositions and perfume andperfumed materials containing at least one of said acetals.

6 Claims. N0 Drawings NOVEL PERFUME COMPOSITIONS AND PERFUMED ARTICLESCONTAINING DI-LOWER ALKYL AND LOWER ALKYLENE ACETALS OF Z-ANI) 3-PHENYLPENTENALS This application is a division of applicantscopending parentapplication Ser. No. 276,922 filed on Aug. 1, 1972 and now abandoned.

BACKGROUND OF THE INVENTION The present invention relates to novelmethods and compositions using certain acetals of 2- or3-phenylpentenals, a number of which are novel themselves, to alter theflavor and/or aroma of consumable materials or act as precursors forfree aldehydes which alter the flavor and/or aroma of consumablematerials.

There has been considerable work performed relating to substances whichcan be used to impart flavors to various consumable materials. Thesesubstances are used to diminish natural materials some of which may bein short supply, and to provide more uniform properties in the finishedproduct. Chocolate flavors, cinnamon flavors, vegetable flavors andhayclover flavors are particularly desirable for many uses in consumablearticles.

3-Phenyl-pentenals have been suggested in U.S. Pat. Application Ser. No.43,555, filed June 4, i970, now U.S. Pat. No. 3,694,232, for use incocoa flavors whereby notes characteristic of milk chocolate areprovided. 3-Phenyl-4-pentenal is indicated to cause the chocolatebeverage to have a fuller, richer sweet milk chocolate flavor. U.S. Pat.No. 3,582,360 issued on June 1, 1971 discloses certain2-phenyl-2-alkenals as being useful for preparing flavoring compositionsand food compositions, particularly those having chocolate or cocoaflavors and/or aroma qualities. Thus, for example, the compound5-methyl-2-phenyl-2-hexenal is indicated therein to alter imitationcocoa flavor so as to provide a more natural cocoa flavor and impart acharacter of bitter chocolate.

Acetals are shown to be useful in fragrance formulations at Column 2,lines 50-65 of U.S. Pat. No. 3,636,l 13. Such acetals have thestructures:

having the structure 2 wherein R is lower alkylene.

In U.S. Pat. Application Ser. No. 43,555 mentioned above, mention ismade of the diethyl acetal of 3-phenyl-4-pentenal and the diethyl acetalof 3-pheny1 3- pentenal; but only as intermediates for producing 3-phenyl-3pentenal and 3-phenyl-2pentenal from 3- phenyl-4-pentenal.

In West et al. Synthetic Perfumes: their Chemistry and Preparation,"published by Edward, Arnold & Co., London, England, in 1949, on page 315cinnamaldehyde dimethyl acetal is stated to have a fine cinnamon-cassiaodor which renders it useful in some Chanel-like fancy perfume and inoriental types like Tabac Blond and Fleur de Tabac". Cinnamaldehydediethyl acetal is also reported. These materials have the followingstructures:

wherein R is methyl or ethyl.

Cinnamaldehyde diethyl acetal is reported in Perfume and FlavorChemicals (Aroma Chemicals)" by S. Arctander (published by the author inMontclair, NJ. l 1969) as having a faint but fresh green slightly spicyoily sweet odor and a mild and oily sweet taste. Arctander goes on tostate: since this acetal like most other acetals is unstable undermildly acid conditions it finds little if any use in flavorcompositions." In addition, Arctander also reports cinnamaldehyde 2,4-dihydroxy-4-methyl-pentane acetal as "soft, tenacious, natural, cinnamontype odor not nearly as harsh as cinnamic aldehyde yet rich and lastingas aldehyde itself." Cinnamic aldehyde dimethyl acetal is also reportedby Arctander and with reference to this acetal Arctander states: Itshould be noted that pure, aldehyde-free acetal is practically colorlessand carries little or no odor similarily to the aldehyde. The ethyleneglycol acetal of cinnamic aldehyde isjndicated by Arctander to be usefulin flavor compositions, such as all spice, cassia, cinnamon, clove andvarious spice blend and it is stated by Arctander to have a sweet spicycinnamon all spice taste not quite as sweet as the aldehyde. It shouldbe noted that cinnamic aldehyde ethylene glycol acetal is on the GRASlist and has been given F.E.M.A. No. 2287.

The cinnamic aldehyde acetals of the prior art are not considered toimpart certain desired qualities to consumable materials which acetalsof 2- and 3-phenylpentenals of this invention are capable of doing asmore specifically described below.

The prior art cinnamic aldehyde acetal noted above, however, beingunsaturated in a position a, B- to the acetal moiety, are relativelyunstable even in aqueous media.

THE INVENTION It has now been discovered that novel solid and liquidfoodstuff and flavoring compositions as well as novel aroma impartingcompositions having rosy and/or sweet woody and/or cinnamon-likecharacteristics found in quality chocolate and cinnamon may be providedby the utilization of certain compounds of the class of di-lower alkylor lower alkylene acetals of 2- and 3-phenyl pentenals. A number ofacetals of this class will also provide sweet green vegetable and cookedtomato note flavors. Still other acetals of our invention. particularly2- and 3-phenyl-2-pentenal lower alkyl and lower alkylene acetals and 3,4 and 5 carbon lower alkyl and lower alkylene acetals of 2- and3-phenylpentenals will act as precursors in forming corresponding freealdehydes which are themselves capable of imparting flavors, such ascinnamon or sweet milk chocolate flavors and nutty notes or cooked tomato and potato flavors or watermelon/cucumber notes to foodstuff; aswell as cocoa aromas or green floral notes, as the case may be, tofragrance formulations. These precursors are uniquely useful in thatthey may be included, preferably, as part of a solid flavor or fragranceimparting composition which is capable of being stored for an indefiniteperiod of time prior to use in a liquid foodstuff or in a perfumeformulation or in a cologne. At the point of ultimate use of the flavoror fragrance imparting material such higher molecular weight acetal orsuch 2- or lphenyl-Z-pentenal lower alkyl or lower alkylene acetal ishydrolyzed due to the presence of other acidic constituents and/or anaqueous medium and due to the liquid phase of the material in which itis used. In addition, it has been found that novel tobacco flavoringcompositions having hay-clover-like qualities with fruity notes orexcellent cinnamon aromas found in quality tobacco may be provided bythe utilization ofa number of compounds of the class of di-lower alkylor lower alkylene acetals of 2- or 3- phenylpentenals. It has furtherbeen determined that novel fragrance compositions having impartedthereto green, rosy characteristics and/or green. balsamic, cinnamicnotes found in quality floral perfume formulations may be provided bythe utilization of a number of compound of the class of di-lower alkylor lower alkylene acetals of 2- or 3-phenyl-pentenals.

The terms phenyl and pentenal as used herein are intended to encompassboth the substituted and unsubstituted derivatives. Thus, either of suchmoieties may contain one or more substituents, the salient requirementbeing that any such substituents be devoid of any tendency todeleteriously affect the functionality of the parent compound havingreference to the ultimate environment contemplated, i.e., a foodstuff orflavoring composition. Thus, with respect to the phenyl moiety, suitablenuclear substituents include lower alkyl and/or lower alkoxy containingfrom 1 to 5 and prefer ably l to 3 carbon atoms. Moreover, suchsubstituent groups may be present in amounts sufficient to provideeither a partially or completely substituted phenyl ring. With respectto the carbon atoms comprising the pentenal chain, lower alkyl of l to 5and preferably 1 to 3 carbon atoms are suitable.

Thus, the di-lower alkyl and alkylene acetals of 2- or 3-phenylpentenals contemplated for use in the practice of the present inventioncanalso, for convenience, be represented according to the followingstructural formula:

wherein one of A or B is of the structure:

wherein R represents hydrogen or lower alkoxy con taining from 1 to 5carbon atoms, R represents hydrogen or lower alkyl containing from I to5 carbon atoms, R and R each represents the same or different loweralkyl containing from i up to 4 carbon atoms; or R and R taken togetherrepresents alkylene having from 2 up to 4 carbon atoms and m and nrepresent integers of l to 5 inclusive, their sum (m+n) being from 2 to7, and wherein one of the wavy lines represents a carbon to carbondouble bond and the othere two lines each represents a carbon to carbonsingle bond, the remaining valence of each carbon atom being satisfiedby at least one member selected from hydrogen and lower alkyl of l to 5carbon atoms. in the foregoing formula, the lower alkyl groups definedby R R and R as well as the lower alkoxy group defined by R may be thesame or different. Specific examples of compounds falling within thescope of the foregoing structural formula include, without necessarylimitation, the following:

3phenyl-3pentenal dimethyl acetal 3-phenyl-3-pentenal ethyl methylacetal 3-phenyl-2-pentenal diethyl acetal 3-phenyl-2-pentenal-l,3-propylene glycol acetal 3-phenyl-4-pentenal diethyl acetal3-phenyl-4-pentenal dimethyl acetal 3'phenyl-4-pentenal ethyl propylacetal 2-phenyl-4-pentenal dimethyl acetal 5-methyl-3-(4-methylphenyl)-4-pentenal ethyl methyl acetal 3-( 3',4',5 '-trimethoxyphenyl)-3-pentenal methyl propyl acetal 3-phenyl-4-methyl-2-pentenal-l,Z-butylene glycol ethwherein one of A or B is a moiety having thestructure wherein R R R R and R are hydrogen or the same or differentlower alkyl; wherein R R11, R R and R are hydrogen or the same ordifferent lower alkyl or the same or different lower alkoxy; wherein R,and R; are separately each C,-C lower alkyl or R and R taken together,is a lower alkylene moiety having from 2 up to 4 carbon atoms; andwherein the wavy lines have the significance previously explained.

As stated previously, the acetal derivatives of 2- or 3-phenyl-pentenalsdescribed herein are capable of supplying, interalia, certain flavor andaroma notes usually lacking in many chocolate, cocoa, vetetable andcinnamon food flavoring materials and tobacco materials heretoforeprovided; thus, the latter materials provided prior to our discoverycharacteristically may yield chocolate flavors and aromas which may becharacterized as thin" and harsh" or may simply have nutty or milkchocolate" notes without the nuances which lend natural notes orcinnamon notes to chocolate or cocoa flavors. By way of contrast, theacetal derivatives of the 2- and 3-phenyl-pentenals of the presentinvention provide, interalia, organoleptic impressions similar to thosewhich are achieved by the addition of natural cinnamon and/or iononematerials and- /or natural damascone to chocolate flavors.

Particularly preferred for use herein are the lower alkyl acetals of3-phenyl-pentenal compounds covered by the foregoing formula whereineach of the valences present in the carbon atoms of the pentenal chain,apart from those necessary to provide single or double bonds, issatisfied by hydrogen and wherein m and n is each one. Such compoundsare represented as follows:

3-phenyl-4-pentenal dialkyl acetals or alkylene acetals3-phenyl-3-pentenal dialkyl acetals or alkylene acetals (wherein R and Rare defined as above).

Examples of food flavor, fragrance, and tobacco flavor properties of thedi-lower alkyl and lower alkylene phenyl pentenal acetals which arepreferred in the practice of the instant invention are as follows:

I. The dimethyl acetal of 3-phenyl-4-pentenal:

Aroma: Cassia, Cinnamon spice-like, with a fresh green" balsamic nuance.

Taste: at 5 ppm has a rosy, cinnamon taste. At [0 ppm has a cinnamonspice-like flavor with rootlike backnotes. At 20 ppm has dominatingcinnamon notes.

Tobacco: at a level of one eighth of 1% imparts a cinnamon powder aroma.

2. The dimethyl acetal of 2-phenyl-4-pentenal:

Aroma: A low keyed greenish note having additional nuances which can bedescribed as haylike, moiety, floral, spicy and having an initial impactof fruity and apple seed aromas.

Taste: At 2 ppm and 5 ppm has a sweet green vegetable low floral andcooked tomato taste. At 10 ppm the taste is more turnipdike. At 1 ppmhas a slight green spicy character.

3. The diethyl acetal of 3-phenyl-4-pentenal;

Aroma: Green, balsamic. cinnamon-like spiciness. Taste: At [0 ppm hasweak rosy notes and a slightly spice-like character with a sweet fruitynuance. Can also be described as having a cinnamon-like character.

Tobacco: At a level of imparts to tobacco a hay-clover-like aroma withfruity notes.

4. The diisobutyl acetal of 3-phenyl-4-pentenal:

Aroma: A low-keyed greenish note.

5. The ethylene glycol acetal of 3-phenyl-4-pentenal: Aroma: Warm sweetcinnamon-spice-like and low keyed green notes with an earthy nuancereminiscent of clovers.

Taste: At 10 ppm has a slight spice-like character reminiscent ofcinnamon or clovers. At l and 2 ppm has a pleasant cinnamon bark taste.At 5 ppm has a cinnamon/clover taste. At 30 ppm has a sweet, fruity, andnotelike taste with mild pungency.

6. The dimethyl acetal of 3-phenyl-3-pentenal:

Aroma: Has a low-keyed green cinnamon note. Examples of food flavorproperties of aldehydes (listed below) for which certain acetals of thisinvention (also listed below) are precursors in aqueous or slight acidic(evg. pH of from 3 up to 7) solution are set forth below:

Acetal Precursor Free Aldehyde Flavor Properties of Free Aldehydes 4methyl-2-phenyl-2 pentenal diethyl acetal 4-methyl 2-phenyl-2- pentenaldiisobutyl acetal 4-methyl-2-phenyl-2 hexenal diethyl acetal 4-methyl2-phenyl-2 hexenal diisobutyl acetal S-methyLZ-phenyl-Z- he xenaldiethyl acetal 5 methyl-2-phenyl-2 hexenal diisobutyl acetalS-methyl-2-( 2,6-dimethylphenyl)-2 hexenal diethyl acetal S-methyl-Z-t2.6-di methylphenyl]-2- hexenal diisobutyl acetal Smethyl-2-(2,4-dimethylphenyl)2- hexenal diethyl acetal 5methyl-2-(2,4-dimethylphenyI)-2- hexenal diisobutyl acetal 5-methyl-2-( 3,S-dimethylphenyl)-2- hexenal diethyl acetal 5-methyl-2-(3.5-dimethylphenyU-L hexenal diisobutyl acetal S-melhyl-2-(4-methylphenyli 2 hexenal diethyl acetal 5-methyl-2-( 4-methylphenyll-2-hexenal diisobutyl acetal 5methyl-2-(isopropylphenyl l-2- hexenaldiethyl acetal 5 methyl2-( isopropylphenylJ-Z- hexenal diisobutyl acetal3-phenyl4-pentenal dissobutyl acetal 4-methyl-2-phenyl-2- pentenal4-methy|-2-phenyl-2 pentenal 4-methyi-2-phenyh2- hexenal4-methyl-2-phenyl-2- hexenal 5-methyl-2-phenyl-2- hexenal S -methyl-2(2,6-di methylphenyU-Z hexenal diethyl acetal 5methyl-2-(2.6-dimethylphenyl)-2- hexenal 5-methyl-2-( 2,4dimethylphenyli-Z- hexenal 5-methyt-2(2.4-dimethylphenyl)-2- hexenalS-rnethyl-2-( 3,5-dimethylphenyU-Z- hexenal 5-methyi-2-( 3,S-dimethylphenyU-L hexenal 5-methyl'2-(4-methylphenyll-Z-hexenal5-methyl-2-(4methylphenyl )-2-hexenal S-methyl-Z-(isopropylphenyl )-2-hexenal S-methyl-Z-(isopropylphenyl)-2 hexenal 3-phenyl-4-pentenalprovides green pungent cocoa flavoring note provides green pungent cocoaflavoring note provides green pungent cocoa flavoring note providesgreen pungent cocoa flavoring note provides green pungent cocoaflavoring note provides green pungent cocoa flavoring note providesgreen pungent cocoa flavoring note provides green pungent cocoaflavoring note provides green pungent cocoa flavoring note providesgreen pungent cocoa flavoring note provides green pungent cocoaflavoring note provides green pungent cocoa flavoring note providesgreen pungent cocoa flavoring note provides green pungent cocoaflavoring note provides green pungent cocoa flavoring note providesgreen pungent cocoa flavoring note sweet milk chocolate As used hereinin regard to flavors, the term alter in its various forms meanssupplying or imparting a flavor character or note to an otherwise bland,relatively tasteless substance, or augmenting the existing flavorcharacteristic where a natural flavor is deficient in erages, dairyproducts, candies, vegetables, cereals,

65 soft drinks, snacks and the like.

In many instances the optimum balance of flavor is obtained by utilizingmixtures of compounds wherein at least one component comprises anunsubstituted lower 9 alkyl or di-lower alkyl acetal of a 2- or3-phenyl-pentenal, i.e., contains no substituents on either the pentenalchain or the phenyl moiety; a second component comprises anunsubstituted 2- or 3-phenyl-pentenal; and a third component comprisesat least one substituted dilower alkyl acetal derivative of a 2- orB-phenyl-pentenal, i.e., an alkyl and/or alkoxy phenyl group. Othermixtures may also include another type of phenyl alkenyl, e.g. a2-phenyl-alkenyl used to, in addition, supply a nutty note. Suchmixtures may comprise, for example, the dimethyl acetal of3-phenyl-4-pentenal; the free aldehyde 3-phenyl-pentenal; and the methylethyl acetal of 3-(4'-methylphenyl)-4-pentenal and/or the dimethylacetal of 3-(4-methoxyphenyl)-4-pentenal. When mixtures of the acetalsof the 2- or 3-phenylpentenal taken together with other phenyl pentenalare used, their proportions with one another can be varied as desired tosuit the particular foodstuff to be flavored and will depend uponwhether the composition so formulated is utilized to supply a totalorganoleptic impression or to enhance or fortify an existing flavor and-/or aroma characteristics. It has been found when preparing cinnamon,chocolate, and cocoa flavors, for example, that a good blend is obtainedby using a mixture of about -20% of a di-lower alkyl acetal of at leastone unsubstituted 3-phenyl-pentenal, e.g. 3-phenyl-4- pentenal dimethylacetal; about 2-5% of a 3-phenylpentenal free aldehyde, e.g.,3-phenyl-4-pentenals;

about 40-50% of at least one 2- or 3-phenyl-pentenal' dialkyl acetalhaving alkyl and/or alkoxy substituents on the phenyl group, e.g.,3-(2',4,6-trimethoxyphenyl)-4-pentenal diethyl acetal,3-(2',3',4'-trimethylphenyl)-3-pentenal diethyl acetal and/or 4-methyl-3-phenyl-2-pentenal l,3-propylene glycol acetal; about 10-20% of atleast one trialkyl substituted 3-phenyl pentenal lower di-alkyl or loweralkenyl acetal, e.g., 3- methyl-3-(2',4'dimethyl-phenyl)-4-pentenall,2-butylene glycol acetal, 4-methyl-3-(2',4'-dimethylphenyl)-Z-pentenal ethyl propyl acetal and/or 4-ethyl-3-(2',4-methylphenyl-Z-pentenal dipropyl acetal, and about -30% of at least onetetraalkyl B-phenyl pentenal lower dialkyl or lower alkylene acetal,e.g., 3-methyl-3- (2',4',6'-trimethyl-phenyl)-4pentenal diethyl acetal.It will be understood that theses ratios can be varied to supply,enhance, modify or fortify the flavor of the foodstuff or flavoringcomposition.

The dialkyl and lower alkylene acetals of 3phenyl pentenals contemplatedfor use in the practice of this invention can be synthesized by firstreacting an appropriately substituted or unsubstituted 3-phenyl-propen-2-ol-l and an appropriately substituted or unsubstituted alkyl vinylether. The reaction can take place using as a catalyst a protonic acid(such as phosphoric acid) thus forming, in one step,3-phenyl-4-pentenal. The desired intermediate products can also beobtained using the aforementioned reactants but using a mercuriccatalyst such as mercuric acetate (in place of the acid catalyst). Sucha procedure is also described by Burgstahler J. Chem. Soc., 1963, pages4986-9 [see paragraph 2 on page 4989]. In addition, another suchprocedure is described in co-pending U.S. Pat. application Ser. No.43,555, filed on June 4, I970. If the 3- phenyl-4-pentenals are producedaccording to the above-mentioned procedures, the di-lower alkyl or loweralkylene acetals are preferably produced therefrom by reacting suchmixtures with a lower alcohol or mixture of lower alcohols or with alower alkylene glycol or mixture of lower alkylene glycols or mixture oflower alcohols and lower alkylene glycols in the presence of an acidcatalyst such as paratoluene sulfonic acid, hydrochloric acid or asource therefor, such as acetyl chloride. 2- or 3-phenylpentenals (freealdehydes) may also be converted to the corresponding acetals byreaction with an appropriate orthoformate. Thus, for example, reactionof triethyl orthoformate with 3-phenyl-4-pentenal will give rise to theproduction of a good yield of the diethyl acetal of 3-phenyl-4-pentenal.Dial kyl acetals of 2- or S-phenyl-pentenals may also be formed byaddition to the free aldehydes with 2,2- dimethoxy propane. Mixtures ofan alkylene glycol such as ethylene glycol and an orthoformate such astriethyl orthoformate give rise to alkylene acetals.

In addition, when producing the aldehydes prior to the reaction withalcohol or with the orthoformate to form the acetal, if only3-phenyl-4-pentenals are formed then the carbon-carbon double bond inthe pentenal moiety of the 3-phenyl-4-pentenal intermediate product, ifdesired, may be rearranged whereby the end product will turn out to bean acetal of a given 3- phenyl-3-pentenal. Thus, initially, the aldehydemoiety may be stabilized by treatment of the 3-phenyl-4- pentenal withan alcohol or a glycol such as methanol, ethanol, l,2-propylene glycol,l,3-propylene glycol. l,2-butylene glycol, 1,3-butylene glycol,1,4-butylene glycol, 2-methyl-l,3-propane diol or ethylene glycol. Theresulting acetal of 3-phenyl-4-pentenal may then be retained and used asa tobacco, food flavor or fragrance adjuvant or it is treated with abase such as potassium t-butoxide whereby a 3-phenyl-3-pentenal acetalis formed. The resultant rearranged acetals may then, if desired, bepurified by means of appropriate extraction and distillation so thatthey are usable as food flavor, fragrance or tobacco flavor adjuvants.The aforementioned reaction sequence is illustrated as follows:

OC,H, Base such as potassium t-butoxide More particularly after they areproduced in the aforementioned manner (e.g. as the 3-phenyI-4-pentenalmixtures or as the 3-phenyl-4-pentenals produced as indicated above orthe alkyl and/or alkoxy substituted derivatives thereof). these freealdehydes are then reacted with a lower alcohol. or a mixture of loweralcohols or a lower alkylene glycol or a mixture of such glycols or amixture of one or more lower alcohols and glycols in the presence of anacidic medium. for example. in the presence of hydrogen chloride or inthe pres ence of a source of hydrogen chloride, such as acetyl chloride.If only 3-phenyl-4 pentenal di-lower alkyl acetals or lower alkyleneglycol acetals are formed, such materials may be desired to be partiallyor entirely rearranged to 3-phenyl-3-pentenal di-lower alcohols or loweralkylene glycol acetals. Predictable mixtures of 3-phenyl- 3pentenalacetals and 3-phenyl-4-pentenal acetals may be produced if desired byshortening the time of reaction by means of prematurely neutralizing thebase (e.g. potassium-t-butoxide) which is present in the reaction mass.

The preparation of 3-phenyl-2-pentenal di-lower alkyl acetals and loweralkylene acetals is most preferably carried out by (ll first forming the3-phenyl-2- pentenal by means of reaction of propiophenone with thelithium salt of a Shiff base of acetaldehyde (e.g. a Shiff base ofacetaldehyde with cyclohexylamine) thereby forming a 3-phenyl-2pentenalShiff base. This Shiff base is then hydrolyzed thus forming theEl-phenyLZ'pentenal (free aldehyde) which is then reacted with asuitable orthoformate and in addition a lower alcohol or a mixture ofdifferent lower alcohols or a lower alkylene glycol or a mixture oflower alkylene glycols or a mixture of alcohols and lower alkylene glycols in the presence of an acidic reaction promoter, thus forming one ora mixture of the lower alkyl acetals and/or alkylene glycol acetalsuseful in our invention. The reaction sequence is illustrated asfollows:

| C H CH +H,C

CIN OH C H C H CH Hydrolysis O ,x H c c IROH [Acid or acid catalyst]IROI CH l 2 H /OR wherein R is lower alkyl, cg methyl, ethyl, propyl orbut 'l.

2 -Phenyl-l-pentenal dialkyl acetals and alkylene glycol acetals of thisinvention are prepared by first preparing the 2-phenyl2-pentenalsaccording to any of the processes set forth in the US. Pat. No.3.582.360 issued on June I. 1971 whereby the free aldehydes areproduced; followed by reacting such free aldehydes with a suitableorthoformate and in addition a desired lower alcohol or lower alkyleneglycol in the presence of an acid such as paratoluene sulfonic acid,aqueous hydrochloric acid, dry HCI gas or acetyl chloride. Anillustration of this reaction is the production of the diethyl acetal of5- methyl-Ltdimethylphenyl )-2-hexenal according to the followingreaction sequence:

H H H oCtHt 2-Phenyl-4-pentenal dialkyl acetals and alkylene glycolacetals of this invention are prepared by first preparing the2-phenyl-4-pentenal free aldehydes. These free aldehydes are prepared byfirst forming the enamine of morpholine and phenylacetaldehyde. Theresulting enamine is then reacted with an allyl halide (such as allylchloride or allyl bromide whereby the allyl moiety is added directly tothe alpha-carbon atom of the enamine; and an immonium salt is formed.Addition of the allyl halide is carried out in the presence of a solventpreferably acetonitrile and in the absence of any catalyst or in thepresence of a potassium or sodium i0- dide catalyst. Both the reactionto form the enamine of phenylacetaldehyde and the reaction to form theimmonium salt are carried out at reflux conditions. The resultingimmonium salt is then hydrolyzed whereby the free aldehyde. the2-phenyl-4-pentenal is produced.

The free aldehydes are then converted to the corresponding dilowcr alkylor lower alkylene acetals by reaetion with a lower alcohol or mixture oflower alco hols or with a lower alkylene glycol or mixture of loweralkylene glycols or mixture of lower alcohols and lower alkylene glycolsin the presence of an acid catalyst, such as paratoluene sulfonic acid,hydrochloric acid or source therefor, such as acetyl chloride. TheZ-phenyl- 4-pentenals may also be converted to the corresponding acetalsby reaction of an appropriate orthoformate. Thus, for example, thereaction of ethyl orthoformate with 2-phenyl-4-pentenal will give riseto the production of a good yield of the diethyl acetal of 2-phenyl-4-pentenal.

The aforementioned reaction sequence is illustrated as follows:

wherein R,, R R and R are C -C lower alkyl and R, is lower alkyl orforms an alkylene glycol acetal ring.

When the materials of this invention, the lower alkyl diacetals andlower alkylene acetals of 2- or 3-phenylpentenals are used as foodflavor adjuvants, the nature of the co-ingredients included with the 2-or 3-phenylpentenal lower dialkyl acetals or lower alkylene acetals informulating the product composition will, i.e., as a foodstuff per se oralternatively as a flavoring composition adapted to be added to afoodstuff at some subsequent point of time. in any event, such compoundsserve to alter the organoleptic characteristics of the ultimatefoodstuff treated therewith.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use being extensivelydescribed in the relevant literature. Apart from the requirement thatany such material be "ingestibly" acceptable, and thus non-toxic orotherwise non-deleterious, nothing particularly critical resides in theselection thereof. Accordingly, such materials, which may in general becharacterized as flavoring adjuvants or vehicles comprise broadly,stabilizers, thickeners, surface active agents, conditioners, flavorantsand flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride,antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2 and 3 tertiarybutyl-4-hydroxyanisole), butylated hydroxy toluene(2,6-di-tertiary-butyl-4- methyl phenol), propyl gallate and the like,sequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar-agar;carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids;carbohydrates; starches pectins, and emulsifiers, e.g., monoanddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose, corn syrup solids and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, monoand diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, turmeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers; anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate, nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Flavorants and flavor intensifiers include organic acids, e.g., fattysaturated acids, unsaturated acids and amino acids; alcohols, e.g.,primary and secondary alcohols; esters, carbonyl compounds includingaldehydes and ketones as well as lactones; cyclic organic materialsincluding benzene derivatives; isocyclics; heterocyclics such as furans,particularly 3-acetyl furan, pyridines, pyrazines (particularlymonoalkyl, dialkyl, trialkyl and tetraalkyl substituted pyrazines) andthe like, sulfur-containing materials including thiazoles, disulfides,thiols, sulfides, aldehydes, (for example, 3- phenyl-4-pentenal,3-phenyl-3-pentenal, 3-phenyl-2- pentenal, 2-phenyl-2-pentenal, and2-phenyl-3-methyl- Z-butenal; disulfides and the like; so-called flavorpotentiators such as monosodium glutamate, guanylates, inosinates,natural and synthetic flavorants such as vanillin, ethyl vanillin,diacetyl, phenethyl Z-furoate, maltol, natural gums and the like;spices, herbs, essential oils and extraetlvfis including bitternessprinciples" such as theobromin, caffcin, naringin and other suitablematerials creating a bitter effect.

The specific flavoring adjuvant selected for use may be either solid orliquid, depending upon the desired physical form of the ultimateproduct, i.e.. foodstuff. whether simulated or natural, and should, inany event, be capable of providing an environment in which the 2- or3-phenyl-pentenal di-lower alkyl acetals or lower alkylene acetals canbe dispersed or admixed to provide a homogeneous medium. In addition,selection of one or more flavoring adjuvants as well as the quantitiesthereof will depend upon the precise organoleptic char acter desired inthe finished product; thus, in the case of flavoring compositions,ingredient selection will vary in accordance with the foodstuff to whichthe flavor and aroma are to be imparted. ln contradistinction, in thepreparation of solid products, e.g., simulated foodstuffs, ingredientscapable of providing normally solid compositions should be selected suchas various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount of 2- or3-phenyl-pentenal di-lower alkyl acetals or lower alkylene acetalsemployed in a particular instance can vary over a relatively wide rangewhereby to achieve desired organoleptic effects having reference to thenature of the product. All parts and percentages given herein are byweight unless otherwise specified. Thus, correspondingly greater amountswould be necessary in those instances wherein the ultimate foodcomposition to be flavored is relatively bland to the taste, whereasrelatively minor quantities may suffice for purposes of enhancing acomposition merely deficient in natural flavor or aroma. Thus, theprimary requirement is that the amount selected be effective, i.e.,sufficient to alter the organoleptic charac teristics of the parentcomposition, whether foodstuff per se or flavoring composition. Thus,the use of insufficient quantities of the 2- or 3-phenyl-pentenaldilower alkyl acetals or lower alkylene acetals will, of course,substantially vitiate any possibility of obtaining the desired resultswhile excess quantities prove needlessly costly and in extreme cases,may disrupt the flavor-aroma balance, thus providing self-defeating.Accordingly, the terminology effective amount and sufficient amount" isto be accorded a significance in the context of the present inventionconsistent with the obtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, it is found thatquantities of 2- or 3-phenyl-pentenal di-lower alkyl acetals or loweralkylene acetals ranging from a small but effective amount, e.g., l.0part per million up to about 200 parts per million by weight based ontotal composition are suitable. Concentrations in excess of the maximumquantities stated are not normally recommended since they fail toprovide commensurate enhancement of organoleptic properties. In thoseinstances wherein the 2- or 3-phenyl-pentanal di-lower alkyl acetals orlower alkylene acetals is added to the foodstuff as an integralcomponent of a flavoring composition, it is, of course, essential thatthe total quantity of flavoring composition employed be sufficient toyield an effective 2- or B-phenyl-pentenal di-lower alkyl acetals orlower alkylene acetals concentration in the foodstuuf product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the 2- or 3-phenyl-pentenal di-lower alkylacetals or lower alkylene acetals in concentrations ranging from about16 to l00% by weight, based on the total weight of said flavoringcomposition.

The compositions described herein can be prepared according toconventional techniques well known in the art for such purposes. Thus,liquid products as typified by cake batters egg nog and chocolate milkcan be formulated by merely admixing the involved ingredients within theproportions stated in a suitable blender to obtain the desiredconsistency, homogeneity of dispersion, etc. Alternatively, flavoringcompositions in the form of particulate solids can be convenientlyprepared by admixing the 2- or 3-phenyl-pentanal di-lower alkyl acetalsor lower alkylene acetals with, for example, gum arabic, gum tragacanth,carrageenan and the like, and thereafter, spray-drying the resultantmixture whereby to obtain the particulate solid product. Prepreparedflavor mixes in powder form e.g., cocoa mix may be obtained by mixingthe dried solid components e.g., milk solids, sugar and the like and 2-,3-, or 4-phenyl-pentenal di-lower alkyl acetals or lower alkyleneacetals in a dry blender until the requisite degree of uniformity isachieved.

It is presently preferred to combine with the 2- or 3- phenyl-pentenaldi-lower alkyl acetals or lower alkylene acetals the following flavoringadjuvants: Vanillin, Maltol, Benzaldehyde and lsovaleraldehyde.

2- or 3-phenyl-pentanal di-lower alkyl acetals and lower alkyleneacetals according to this invention can also be used to improve andaugment the organoleptic properties of tobacco and tobacco products.Thus, for example, 3-phenyl-4-pentena] di-ethyl acetal will impart adesired hay clover-like flavor with fruity notes to a standard cloverflavor used in tobacco, Tobacco, as used herein, includes naturaltobaccos, such as burley, Turkish tobacco, Maryland tobacco;tobacco-like products, such as reconstituted tobacco of homogenizedtobacco; and tobacco substituents intended to replace natural tobaccosuch as various vegetable leaves, for example, lettuce and cabbageleaves and the like.

A 2- or B-phenyLpentenal di-lower alkyl acetal or lower alkylene acetalof this invention and an auxiliary perfume ingredient, including, forexample, alcohols, aldehydes, nitriles, esters, cyclic ethers, andnatural essential oils, which are admixed so that the combined odors ofthe individual components produce a pleasant or desired fragrance. Suchperfume compositions usually contain (a) the main note or the "bouquetor foundation stone of the composition; (b) modifiers which round offand accompany the main note; (c) fixatives which include odoroussubstances which lead a particular note to the perfume throughout allstages of evaporation and substances which retard evaporation; and (d)topnotes which are usually low boiling fresh smelling materials.

In perfume compositions the individual component will contribute itsparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum of the effects of each of theingredients. Thus, the individual compounds of this invention, ormixtures thereof, can be used to alter the aroma characteristics of aperfume composition, for example, by utilizing or moderating theolfactory reaction contributed by another ingredient in the composition.

The amount of the acetal compound of this invention which will beeffective in perfume compositions depends in many factors, including theother ingredients, their amounts and the effects which are desired. ithas been found that perfume compositions containing as little as 1% ofthe compounds of this invention or even less, can be used to impart ascent odor to soaps, cosmetics, and the other products. The amountemployed can range up to of the fragrance components and will depend onconsiderations of cost, nature of the end product, the effect desired onthe finished product and the particular fragrance sought.

The 2- and 3-phenyl-pentanal di-lower alkyl acetals and lower alkyleneacetals of this invention are useful in a perfume composition as anolfactory component in detergents and soaps; space odorants anddeodorants; perfumes; Colognes; toilet waters; bath preparations, suchas bath oils and bath solids; hair preparations, such as lacquers,brilliantines, pomades and shampoo; cosmetic preparations, such ascreams, deodorants, hand lotions, and sun screens; powders, such astalcs, dusting powders, face powders and the like. When used as anolfactory component of a perfumed article, as little as 100 ppm of oneor more of the preferred acetals of this invention will suffice toimpart either a green, balsamic, cinnamic-like character to the topnoteof the fragrance employed or a green. rosy character to the topnote ofthe fragrance employed or a green, rosy note to the body of thefragrance employed. Generally, no more than 0.5% of the acetals of thisinvention based on the ultimate end product is required in the perfumecomposition.

In addition, the perfume composition or fragrance composition of thisinvention can contain a vehicle or carrier for the acetals alone or withother ingredients. The vehicle can be a liquid such as an alcohol,nontoxic alcohol, non-toxic glycol, or the like. The carrier can also bean absorbent solid, such as a gum (e.g. gum arabic) or components forencapsulating the composition (such as gelatin).

it will thus be apparent that the acetals according to the presentinvention can be utilized to alter the sensory property, particularlyorganoleptic properties, such as flavor and/or fragrance ofa widevariety of consumable materials.

The following Examples are given to illustrate embodiments of theinvention as it is presently preferred to practice it. It will beunderstood that these Examples are illustrative, and the invention isnot to be considered as restricted thereto except as indicated in theappended claims.

EXAMPLE I Preparation of 3-phenyl-4-pentenal dimethyl acetal 18 grams of3-phenyl-4-pentenal produced according to the procedure Burgstahler J.Chem. Soc. 1963, pages 4986-90 is admixed with 16 grams of Linde 3Amolecular sieves one-sixteenth inch pellets purchased from the Matheson,Coleman & Bell Co., East Rutheford, N.J., and combined with 115 ml. ofanhydrous methanol. In a separate flask 1 ml. of acetyl chloride isdissolved in 8 ml. of methanol whereby an HClmethanol solution isformed. The resulting HCl solution is then added to the3-phenyl-4-pentenal solution (total volumezl25 ml.) After a period oftwo hours, the resultant reaction mixture is decanted from the molecularsieves, evaporated and distilled at a pressure of 0.5 mm. Hg. and atemperature in the range of 7273C. The distillate is 3-phenyl-4-pentenaldimethyl acetal.

The NMR data is as follows:

Preparation of 3-phenyl-3-pentenal dimethyl acetal 15 grams of the3-phenyl-4-pentenal dimethyl acetal produced in the immediatelypreceding Example is dissolved in dimethyl sulfoxide (total volume 50ml.) and 1.5 grams of potasssium-t-butoxide is added. The mixture isthen stored at room temperature under a nitrogen blanket for a period of1% hours. The reaction mass is then diluted with 50cc of water and isextracted with two ml. portions of diethyl ether. The diethyl etherextract is dried over anhydrous sodium sulfate and evaporated down. Theresulting residue contains a 2:1 mixture of 3-phenyl-3-pentenal dimethylacetal and 3-phenyl-4-pentenal dimethyl acetal. The resulting mixture isthen retracted with potassium-t-butoxide in dimethyl sulfoxide and againworked up as above. Re moval of solvent yields 14.9 grams of a quitemobile orange oil. The reaction product is distilled at 83C and 0.1 mm.Hg. pressure in a concentric tube distillation apparatus, yielding3-phenyl-3-pentenal dimethyl acetal.

The NMR data for this compound is as follows:

EXAMPLE llI Preparation of 3-Phenyl2-pentenal Into a 100 ml. flask thefollowing ingredients are added:

Ingredients Quantity Piperidine 10.0 ml. Diethyl ether 10.0 ml.

62.5 ml. of a 1.6 N butyl lithium solution in hexane is added dropwise.After the addition 12.5 grams of the Schiff base of acetaldehyde andcyclohexylamine (boiling point 5256C at 20 mm.Hg. pressure) having thestructure:

is added as a solution in 20 ml. of diethyl ether. The resulting mass ismaintained at approximately 0C with the use of an ice bath. After about15 minutes, the reaction mass is cooled in a dry ice isopropyl alcoholbath and 9.0 ml. propiophenone is added dropwise. The reaction mass isstored overnight at room temperature under a blanket of nitrogen. 150ml. of water is then added to the reaction mass with stirring yielding atwo-phase reaction mass: an aqueous phase and an organic phase. Theorganic phase is separated and dried over anhydrous sodium sulfate andevaporated down to an orange oil. The said oil is admixed with 50 gramsof oxalic acid dissolved in 150 ml. The resulting mixture is steamdistilled for a period of two hours. Both the resi due and steamdistillate are extracted with 200 ml portions of diethyl ether and theether extracts are combined, dried over anhydrous sodium sulfate andevaporated down yielding 7.34 grams of an orange oil. This materialcontains both the cis and trans-isomers of 3- phenyl-2-pentenal, whichare isolated in admixture by means of preparative gas-liquidchromatography.

EXAMPLE IV 18 Grams of the 3-phenyl-2-pentenal produced according to theprocedure of Example III is admixed with 16 grams of triethylorthoformate and a solution formed by adding two drops of acetylchloride to 1 15 ml. of anhydrous ethanol in a 250 ml. flask equippedwith stirrer. thermometer, and reflux condenserv The reaction mass isstored for a period of two hours and is then decanted. The reaction massis evaporated down yielding the diethyl acetal of 3-phe11yl-2-pentenal.

EXAMPLE V The following mixture is prepared:

Ingredients Parts 3-Phenyl-4-pentenal dimethyl acetal 83-Phenyl-3-pentenal dimethyl acetal l Ylarlg extra l0 Geraniol coeur 50Citronellol coeur l00 Dimethyl benzyl carbinol l Phenyl ethyl alcoholcoeur 50 Hexyl cinnamic aldehyde 40 Z-n-heptyl-cyclopentanone 5 Dielsalder addition product of cyclopentadiene and 3-methyL3-penten-2-onehaving the structure The 3-phenyl-4-pentenal dimethyl acetal imparts tothis green Nasturtian fragrance a green, balsamic, cinnamic-liketopnote. The 3-phenyl-3-pentenal dimethyl acetal imparts a green, rosycharacter to the topnote of this fragrance formulation.

20 EXAMPLE VI The following mixture is prepared Ingredients Parts3-Phenyl-4-pentenal ethylene acetal 3 3-Phenyl-4-pentenal diisobutylacetal 4 2-oxa-l,l.3,3-tetramethyl-2,3,5,6,7.8

hexahyclrol H-benz(f)-indene 3 Ylang extra 5 Geraniol coeur l00Citronellol coeur Dimethyl benzyl carbinol 20 Phenyl ethyl alcohol coeur30 Hexyl cinnamic aldehyde 30 2-n-heptyl-cyclopentanone 2 Diels Alderaddition product of cyclopentadiene and 3-methyI-3-penten-2-one havingthe structure The use of the 3phenyl-4-pentenal ethylene acetal impartsto the topnote of this green floral fragrance a green, rosy note; andthe 3-phenyl-4-pentenal diisobuty] acetal imparts to the body ofthisfragrance a green, rosy note.

EXAMPLE Vll A tobacco flavoring formulation is prepared by admixing thefollowing ingredients:

Ingredients Parts Cinnamaldehyde 30.60 Nutmeg oil El 050 Dibenzyl ether3.70 Eugenol [.20 Coumarin 3.00 Vanillin 1.00 3Phenyl-4-pentenal-dimethyl acetyl 60.00

This material is added to smoking tobacco at the rate of 006-0. [5% ofthe weight of the tobacco.

The use of the 3-phenyl-4-pentenal dimethyl acetal provides to theflavor an excellent cinnamon powder aroma and causes the overall flavorto impart a cinna mon character to tobacco. Without the use of the 3-phenyl-4-pentenal dimethyl acetal cinnamon flavor of this material isbland and lacks body.

EXAMPLE VIII A tobacco flavoring formulation is prepared by admixing thefollowing ingredients:

The foregoing flavor is added to smoking tobacco at the rate of 0.100.30% of the weight of tobacco. The use of the 3-phenyl-4-pentenaldiethyl acetal in the flavor causes the tobacco to have a hay-cloverlike flavor with fruity notes.

EXAMPLE [X The following mixture is prepared:

Ingredients Parts 3-Phenyl-4-pentenal dimethyl acetal produced accordingto the procedure of Example l Cinnamic aldehyde Orange oil Oil of clovesPhenyl ethyl alcohol Ethyl alcohol on Out-.0000:

The addition of the 3-phenyl-4-pentenal dimethyl acetal to this mixtureimparts to the flavor a dominating full bodied cinnamon aroma. Withoutthe 3-pheny1-4- pentenal dimethyl acetal, the flavor formulation isbland, lacks body and requires approximately three times as muchmaterial when added to the standard cinnamon flavor powders for use inpastry powders and cake powders. The subject flavor formulation acts asan absolute replacement for cinnamon bark, Ceylon (Cortex cinnamoniceylanici) when used as a flavor in baking. Thus, 420 grams of theabovementioned flavor formulation are added to the following powder cakeflavor oil which is then added at the rate of 0.25% to standard cake mixand appropriately baked:

Mixture of Gm. 27.5 ethyl vanillin 126.0 vanillin 66.0 oil of bitteralmond 420.0 oil of cinnamon bark 66.0 oil of cloves 33.0 oil ofcardamom 66.0 oil of nutmeg I955 oil of lemon, cold pressed Total 10000EXAMPLE X Preparation of 2-Phenyl-4-Pentenal Into a SOO-liter flaskequipped with a stirrer, thermometer, water separator, reflux condenser,heating mantle and addition funnel the following materials are added:

8.8 grams morpholine 250 ml benzene 12.0 grams phenylacetaldehyde Themixture is refluxed with water separation until no more water isproduced from the reaction mixture (period of time: 4 hours). Thebenzene is then evaporated leaving a yellow solid which is thendissolved in 200 ml. acetonitrile. The acetonitrile acts as a solvent.

The resulting enamine reaction product having the structure:

dissolved in acetonitrile is then admixed with 9.0 ml. of allylchloride. 0.25 Grams of K1 (solid) is added and the reaction mixture isthen refluxed with stirring for a period of 12 hours. The acetonitrilesolvent is then removed by means of adding the reaction mixture to arotary evaporator. The reaction mass which now contains the immoniumsalt having the structure:

is placed in a 500-ml three-neck flask equipped with stirrer,thermometer and reflux condenser. 300 ml. of l.5M aqueous hydrochloricacid is added and the reaction mass is stirred for a period of 3 hours.The reaction mass is then placed in a one liter separatory funnel andextracted with three 200 ml. portions of diethyl ether. The diethylether is washed successively with 200 ml portions of water and saturatedsodium carbonate. The resulting ether extract is then dried overanhydrous sodium sulfate and evaporated thereby yielding a residual redoil. This red oil is rushed over at 0.2 ml mercury pressure yieldingl.70 grams of yellow oil. This material is then passed through a 10 footinches SE-30 GLC column. IR, mass spectral and NMR analysis confirm thestructure of this material as '2-phenyl-4-pentenal.

The NMR data for this compound is as follows:

Preparation of 2-Phenyl-4-Pentenal Dimethyl Acetal 300 Mg. of2-phenyl-4-pentenal produced in Example X is dissolved in l0 ml. ofmethanol and 0.5 grams of 2,2-dimethoxy propane. One drop of acetylchloride is added to the reaction mixture and the mixture is ppmInterpretation 7.20 lm) SH Aromatic protons 5.80-5.40 (m) IH Olefinicproton 5.00-4.80 (m) 2H Oleflnic proton 4.40 (d) IH Acetal proton 3.34ts) 3H CH ;O- 3.20 is) 3H CH:O 2.92 lm) lH Ben ylic proton 2.50 1m) 2HArylC-CH, C=C

EXAMPLE XII 2-Phenyl-4-pentenal dimethyl acetal is added directly to afood product prior to processing and canning. The following illustratesthe beneficial flavor effect when 2-phenyl'4-pentenal dimethyl acetal isadded directly to several food products just prior to their consumption.

i. In tomato soup at -20 ppm: creates a distinctive flavorcharacteristics in the product; has an aroma characterized as sweet,green, vegetable, raw carrot, cooked tomato and turnip-like.

ii. In blended vegetable sauce at approximately 30 brings up turnip andraw carrot notes but depresses celery note and blends flavor in adesirable manner thereby providing an increase in turnip and cookedtomato flavor.

iii. In vegetable soup at 40 ppm:

imparts a fresh vegetable flavor; the turnip and raw carrot and cookedtomato notes give the entire vegetable flavor a very full body.

iv. In bean tomato sauce at approximately ppm:

modifies the flavor by reducing the harsh character of the tomato spicemixture while at the same time adding turnip and raw carrot notes anddeveloping the typical cooked tomato note.

The levels of concentration of the 2-phenyl-4-pentenal dimethyl acetalmay be reduced by when 2- isobutyl thiazole is added at the rate of 5ppb in addition to the 2-phenyl-4-pentenal dimethyl acetal to thevarious products set forth above. It should be understood further thatnoticeable differences in the flavor are discernable at otherconcentrations. At much higher levels, the flavor becomes objectionableand overly rancid tasting (eg. 200O ppm).

EXAMPLE XIII Preparation of 3-Phenyl-4-Pentenal Diethyl Acetal3-phenyl-4 pentenal diethyl orthoformate 4.80 grams 6.00 grams 24Absolute ethanol having dissolved therein hydrogen chloride (produced byadding 0.l ml

acetyl chloride to It) ml of absolute ethanoll 10 ml.

The mixture warms spontaneously within 5 minutes. After stirring for onehour the volatile materials are then evaporated and the residualmaterial is distilled yielding 5.88 grams of a colorless materialboiling at 6870% at 0.] mm Hg pressure. NMR, IR and mass spectralanalysis indicate that this material is 97% 3- phenyl-4-pentenal diethylacetal.

The NMR data for this compound is as follows:

ppm Interpretation 7.35-7.14 (m) 5H Aromatic protons 6.12-5.78 (m) 1HOlefinic proton 5.l()4. )6 (m) 2H Olefinic protons 4.33 (t) 1H Acetalproton 3.75432 lm) 4H Protons alpha to EXAMPLE XIV Preparation of3-Phenyl-4-Pentenal Ethylene Acetal Into a 100-ml flask equipped withthermometer. water separator, stirrer and reflux condenser, thefollowing materials are added:

3-phenyl-4-pentenal 8.00 grams Ethylene glycol 5.00 grams Benzene 40 ml.Paratoluene sulfonic acid 0.5 grams The reaction mixture is refluxeduntil water is no longer evolved therefrom (one hour). The reactionmixture is then transferred to a 250 ml. separatory funnel and theheavier phase is discarded. The benzene phase is then washed with three100 ml portions of saturated sodium bicarbonate. The resulting solutionis then dried over anhydrous sodium sulfate and evaporated until acolorless oil residue is obtained. This residue is evaporated at 0.04mm. Hg pressure at a temperature of 7983C yielding 5.5! grams ofproduct. The product is confirmed by IR, NMR and mass spectral analysisas 3-phenyl-4-pentenal ethylene acetal having the structure:

The NMR data for this compound is as follows:

ppm interpretation 7.24 (m) H Aryl protons 6.26-5.80 (m) ll-l Olefinieproton 514-498 (m) 2H Olefinic protons 4.72 (t) 1H Acetal proton4.00-3.74 (m) 4H O-CH,CH,-O'

2.08 and L98 (2 doublets) 2H Aryl-C-Clk-CO EXAMPLE XV Preparation of3-Phenyl-4-Pentenal Diisobutyl Acetal Into a 25 ml flask equipped withmagnetic stirrer, thermometer, reflux condenser and water separator, thefollowing materials are placed:

3-Phenyl-4-pentenal 8.00 grams lsobutyl alcohol 16.00 grams Anhydrousbenzene 25 ml. Paratoluene sulfonic acid 0.2 grams The reaction mass isthen refluxed while water is being removed for a period of 15 minutes.The refluxing continues for a period of one additional hour. Theresulting solution is then washed with 100 ml. of saturated sodiumcarbonate solution and dried over anhydrous sodium sulfate. The benzeneis evaporated and the residual colorless oil is distilled at 110C(0.l0-0.l5 mm. Hg pressure) providing 6.66 grams of product having apurity greater than 95%. NMR, [R and mass spectral analysis yield theinformation that the product is 3-phenyl-4-pentena1 diisobutyl acetal.

The NMR data for this compound is as follows:

It will be understood by those skilled in the art from the foregoingdescription that the 2- or B-phenyl-pentenals lower alkyl and loweralkylene acetals can be used in the preparation of a wide variety offlavor and fragrance compositions. The acetals prepared according to theseveral examples can be used in a manner similar to those shown in thevarious flavoring, perfume and 26 tobacco examples.

What is claimed is:

l. A process for altering the aroma properties of consumable materialselected from the group consisting of perfume compositions and perfumedarticles which comprises adding thereto a small but effective amount ofat least one acetal having the structure:

wherein one of A or B is of the structure:

wherein R represents hydrogen or lower alkoxy containing from I to 5carbon atoms, R represents hydrogen or lower alkyl containing from I to5 carbon atoms, R, and R each represents the same or different loweralkyl containing from 1 up to 4 carbon atoms; or R, and R, takentogether represents alkylene having from 2 up to 4 carbon atoms and mand n represent integers of l to 5 inclusive, their susm (m+n) beingfrom 2 to 7, and wherein one of the wavy lines represents a carbon tocarbon double bond and the other two lines each represents a carbon tocarbon single bond, the remaining valence of each carbon atom beingsatisfied by at least one member selected from hydrogen and lower alkylof l to 5 carbon atoms.

2. A process according to claim 1 wherein the consumable material is asoap, detergent, cosmetic, space odorant, space deodorant, or perfumecomposition.

3. A process according to claim 1 wherein said acetal is3-phenyl-4-pentenal dimethyl acetal.

4. A process according to claim 1 wherein said acetal is3-phenyl-4-pentenal diethyl acetal.

5. A process according to claim 1 wherein said acetal is2-phenyl-4-pentenal dimethyl acetal.

6. A fragrance modifying composition containing at least one acetalaccording to claim 1 and an auxiliary perfume ingredient.

* t i i

1. A PROCESS FOR ALTERING THE AROMA PROPERTIES OF CONSUMABLE MATERIALSELECTED FROM THE GROUP CONSISTING OF PERFUME COMPOSITIONS AND PERFUMEDARTICLES WHICH COMPRISES ADDING THERETO A SMALL BUT EFFECTIVE AMOUNT OFAT LEAST ONE ACETAL HAVING THE STRUCTURE:
 2. A process according toclaim 1 wherein the consumable material is a soap, detergent, cosmetic,space odorant, space deodorant, or perfume composition.
 3. A processaccording to claim 1 wherein said acetal is 3-phenyl-4-pentenal dimethylacetal.
 4. A process according to claim 1 wherein said acetal is3-phenyl-4-pentenal diethyl acetal.
 5. A process according to claim 1wherein said acetal is 2-phenyl-4-pentenal dimethyl acetal.
 6. AFRAGRANCE MODIFYING COMPOSITION CONTAINING AT LEAST ONE ACETAL ACCORDINGTO CLAIM 1 AND AN AUXILIARY PERFUME INGREDIENT.